If its a normal modern system could be a faulty motorised valve passing when just HW on, or stuck in the open position and operating the microswitch causing boiler and pump to stay on even if clock set to off. If old fashioned gravity system and the rads( usually just up stairs ) are heating when just HW on it will be your anti gravity valve gone ,about 3 inches long fitted on flow pipe from boiler usually within a couple of feet of boiler
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